US4576995A - Laminated article and production thereof - Google Patents

Laminated article and production thereof Download PDF

Info

Publication number: US4576995A
Authority: US; United States
Prior art keywords: ethylene; vinyl acetate; adhesive; copolymer; acetate copolymer
Prior art date: 1983-07-22
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Fee Related

Application number

US06/633,426

Other languages

English (en)

Inventor

Masamitsu Nakabayashi

Yuzo Furukawa

Akira Tashiro

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Takeda Pharmaceutical Co Ltd

Original Assignee

Takeda Chemical Industries Ltd

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1983-07-22

Filing date

1984-07-19

Publication date

1986-03-18

1984-07-19 Application filed by Takeda Chemical Industries Ltd filed Critical Takeda Chemical Industries Ltd

1984-07-19 Assigned to TAKEDA CHEMICAL INDUSTRIES, LTD. reassignment TAKEDA CHEMICAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: FURUKAWA, YUZO, NAKABAYASHI, MASAMITSU, TASHIRO, AKIRA

1986-03-18 Application granted granted Critical

1986-03-18 Publication of US4576995A publication Critical patent/US4576995A/en

2004-07-19 Anticipated expiration legal-status Critical

Status Expired - Fee Related legal-status Critical Current

Links

238000004519 manufacturing process Methods 0.000 title abstract description 4
229920001577 copolymer Polymers 0.000 claims abstract description 82
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 55
239000005977 Ethylene Substances 0.000 claims abstract description 55
239000000853 adhesive Substances 0.000 claims abstract description 39
230000001070 adhesive effect Effects 0.000 claims abstract description 39
239000004793 Polystyrene Substances 0.000 claims abstract description 25
229920002223 polystyrene Polymers 0.000 claims abstract description 25
125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 17
PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 25
150000008064 anhydrides Chemical class 0.000 claims description 10
FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
239000000155 melt Substances 0.000 claims description 8
238000012986 modification Methods 0.000 claims description 3
230000004048 modification Effects 0.000 claims description 2
150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 6
229920002554 vinyl polymer Polymers 0.000 abstract description 17
150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract description 17
239000000178 monomer Substances 0.000 abstract description 16
125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 16
239000000463 material Substances 0.000 abstract description 13
239000011229 interlayer Substances 0.000 abstract description 6
230000004888 barrier function Effects 0.000 abstract description 3
230000032798 delamination Effects 0.000 abstract description 3
235000013305 food Nutrition 0.000 abstract description 3
238000004321 preservation Methods 0.000 abstract description 2
238000000034 method Methods 0.000 description 18
239000000047 product Substances 0.000 description 12
239000011347 resin Substances 0.000 description 10
229920005989 resin Polymers 0.000 description 10
239000010410 layer Substances 0.000 description 9
238000007334 copolymerization reaction Methods 0.000 description 8
238000006116 polymerization reaction Methods 0.000 description 8
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
238000001125 extrusion Methods 0.000 description 6
CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
239000002904 solvent Substances 0.000 description 5
-1 vapor Substances 0.000 description 5
239000008096 xylene Substances 0.000 description 5
239000000203 mixture Substances 0.000 description 4
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
239000004342 Benzoyl peroxide Substances 0.000 description 3
OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
235000019400 benzoyl peroxide Nutrition 0.000 description 3
238000010528 free radical solution polymerization reaction Methods 0.000 description 3
229920000578 graft copolymer Polymers 0.000 description 3
238000010559 graft polymerization reaction Methods 0.000 description 3
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
239000008188 pellet Substances 0.000 description 3
229920000098 polyolefin Polymers 0.000 description 3
239000000758 substrate Substances 0.000 description 3
OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
239000004698 Polyethylene Substances 0.000 description 2
239000004743 Polypropylene Substances 0.000 description 2
150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
239000012933 diacyl peroxide Substances 0.000 description 2
238000007720 emulsion polymerization reaction Methods 0.000 description 2
238000009472 formulation Methods 0.000 description 2
235000013611 frozen food Nutrition 0.000 description 2
239000007789 gas Substances 0.000 description 2
238000007731 hot pressing Methods 0.000 description 2
150000001451 organic peroxides Chemical class 0.000 description 2
150000002978 peroxides Chemical class 0.000 description 2
229920000573 polyethylene Polymers 0.000 description 2
229920001155 polypropylene Polymers 0.000 description 2
239000007870 radical polymerization initiator Substances 0.000 description 2
238000003756 stirring Methods 0.000 description 2
VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
239000012790 adhesive layer Substances 0.000 description 1
150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
239000003963 antioxidant agent Substances 0.000 description 1
239000002216 antistatic agent Substances 0.000 description 1
150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
229920005601 base polymer Polymers 0.000 description 1
125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
238000012662 bulk polymerization Methods 0.000 description 1
238000006243 chemical reaction Methods 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
239000002537 cosmetic Substances 0.000 description 1
238000004132 cross linking Methods 0.000 description 1
230000003247 decreasing effect Effects 0.000 description 1
LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
150000001991 dicarboxylic acids Chemical class 0.000 description 1
239000003814 drug Substances 0.000 description 1
239000000839 emulsion Substances 0.000 description 1
230000001747 exhibiting effect Effects 0.000 description 1
239000000945 filler Substances 0.000 description 1
239000010408 film Substances 0.000 description 1
238000001914 filtration Methods 0.000 description 1
239000001530 fumaric acid Substances 0.000 description 1
125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
239000008187 granular material Substances 0.000 description 1
239000012760 heat stabilizer Substances 0.000 description 1
229920001519 homopolymer Polymers 0.000 description 1
230000007062 hydrolysis Effects 0.000 description 1
238000006460 hydrolysis reaction Methods 0.000 description 1
239000003999 initiator Substances 0.000 description 1
229920000554 ionomer Polymers 0.000 description 1
239000003350 kerosene Substances 0.000 description 1
239000004611 light stabiliser Substances 0.000 description 1
VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
239000011976 maleic acid Substances 0.000 description 1
229910021645 metal ion Inorganic materials 0.000 description 1
LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
238000000465 moulding Methods 0.000 description 1
239000012299 nitrogen atmosphere Substances 0.000 description 1
239000003960 organic solvent Substances 0.000 description 1
239000001301 oxygen Substances 0.000 description 1
229910052760 oxygen Inorganic materials 0.000 description 1
239000005022 packaging material Substances 0.000 description 1
125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
239000003208 petroleum Substances 0.000 description 1
229920000642 polymer Polymers 0.000 description 1
239000002861 polymer material Substances 0.000 description 1
239000003505 polymerization initiator Substances 0.000 description 1
239000000843 powder Substances 0.000 description 1
239000012254 powdered material Substances 0.000 description 1
239000002244 precipitate Substances 0.000 description 1
239000011541 reaction mixture Substances 0.000 description 1
238000007127 saponification reaction Methods 0.000 description 1
239000000243 solution Substances 0.000 description 1
239000000725 suspension Substances 0.000 description 1
238000010557 suspension polymerization reaction Methods 0.000 description 1
238000003786 synthesis reaction Methods 0.000 description 1
OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
230000037303 wrinkles Effects 0.000 description 1

Classifications

- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified

Definitions

the present invention relates to an adhesive exhibiting excellent adhesion to an ethylene/vinyl alcohol copolymer and polystyrene, to a laminated article having the adhesive as an interlayer and to the production thereof.
Ethylene/vinyl alcohol copolymers owing to their excellent clarity and gas barrier properties toward water, vapor, oxygen, etc., have been widely used as packaging materials in such areas as foods, pharmaceuticals and cosmetics in the form of their laminates with a polyolefin such as polyethylene or polypropylene.
a polyolefin such as polyethylene or polypropylene.
processability problems such as lack of clarity, appearance of wrinkles on the bottom of the container and appearance of curls at the sealed portions.
their laminates with polystyrene are suitable as a deep drawing material, but there has not been found out any adhesive which exhibits satisfactory performance in the production of the laminates.
adhesives As the adhesive for bonding ethylene/vinyl alcohol copolymers and polyolefins together, various adhesives have been put into practical use. These adhesives include, for example, modified polyolefins (e.g., polyethylene, polypropylene, an ethylene/vinyl acetate copolymer with a higher content of ethylene) which are subjected to graft-modification with an unsaturated carboxylic acid or its anhydride; copolymers from ethylene and an unsaturated carboxylic acid or ionomer resins obtained by crosslinking the copolymers with metal ions; ethylenic copolymers having glycidyl groups; and hydrolysis products of an ethylene/vinyl acetate copolymer.
modified polyolefins e.g., polyethylene, polypropylene, an ethylene/vinyl acetate copolymer with a higher content of ethylene
the present inventors after their intensive study on such adhesives, found that such modified ethylene/vinyl acetate copolymers as obtained by graft-copolymerizing styrene and maleic anhydride to ethylene/vinyl acetate copolymers exhibit excellent performance in bonding ethylene/vinyl alcohol copolymers and polystyrene.
the present invention has been completed based on the finding and further study.
An adhesive for bonding an ethylene/vinyl alcohol copolymer and polystyrene together which comprises a modified ethylene/vinyl acetate copolymer obtained by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to an ethylene/vinyl acetate copolymer,
a laminated article which consists of an ethylene/vinyl alcohol copolymer and polystyrene and has a modified ethylene/vinyl acetate copolyemr obtained by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to an ethylene/vinyl acetate copolymer as its adhesive interlayer, and
a process for producing a laminated article which comprises (a) forming an ethylene/vinyl alcohol copolymer material and polystyrene material into a sheet, respectively and sandwiching between the sheets an adhesive which comprises a modified ethylene/vinyl acetate copolymer obtained by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to an ethylene/vinyl acetate copolymer, followed by hot-pressing, or (b) coextruding an ethylene/vinyl alcohol copolymer material and polystylene material together with an adhesive which comprises a modified ethylene/vinyl acetate copolymer obtained by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to an ethylene/vinyl acetate copolymer.
a base polymer for the modified products is an ethylene/vinyl acetate copolymer which is the known copolymer.
the copolymer can be produced, for example, by the high-pressure polymerization in which ethylene and vinyl acetate are polymerized at 1000 to 2000 atmospheric pressure or by the solution or emulsion polymerization, the polymerizations being carried out in the presence of an organic solvent as a medium at 300 to 400 atmospheric pressure.
the component for the adhesive according to the present invention is a modified product produced by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to the copolymer.
styrenic vinyl monomer mention can be made of, for example, styrene, p-methylstyrene, ⁇ -methylstyrene, etc., and particularly styrene is preferably used.
⁇ , ⁇ -unsaturated carboxylic acid mention can be made of, for example, an acrylic vinyl monomer such as acrylic acid and methacrylic acid or an ⁇ , ⁇ -unsaturated dicarboxylic acid or anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride, and particularly maleic anhydride is preferably employed.
the amount of the ⁇ , ⁇ -unsaturated carboxylic acid to be used is such that the ratio of the ⁇ , ⁇ -unsaturated carboxylic acid to a modified copolymer obtained by graft-copolymerizing the styrenic vinyl monomer and the ⁇ , ⁇ -unsaturated carboxylic acid may be 0.05 to 10 weight %, preferably 0.5 to 5 weight %, and the styrenic vinyl monomer is employed in the proportion of about 0.8 to 1.2 moles per mole of the ⁇ , ⁇ -unsaturated carboxylic acid.
the conventional graft polymerization technique can be employed and the graft-polymerization is carried out in the presence of a radical polymerization initiator.
dialkyl organic peroxides such as dialkyl peroxides exemplified by dicumyl peroxide, di-t-butyl peroxide, etc., peroxy esters exemplified by t-butyl peroxybenzoate, t-butyl peroxyoctoate, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, etc.
the radical initiator is employed at the ratio of about 0.1 to 10 weight % againt the ethylene/vinyl acetate copolymer. Furthermore, it is desirable to conduct the polymerization at a temperature in the range from ambient temperature to 150° C.
the polymerization can be achieved by employing a solution, suspension, emulsion or bulk polymerization method.
the solvent employable as the solvent are aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as kerosene, hexane and petroleum ether, and chlorinated hydrocarbons such as 1,2-dichloroethane.
the amount of the solvent is generally from 1/2 to 5 times by weight that of the base copolymer.
a non-solvent is added to the reaction solution in an amount of 1/2 to 3, preferably 0.9 to 1.3 times the solvent volume used.
the non-solvent includes a monohydric alcohol such as methanol and ethanol. The precipitates are gathered to obtain a modified ethylene/vinyl acetate copolymer product.
the adhesive according to the present invention comprises the modified ethylene/vinyl acetate copolymer product obtained by the above procedure.
the modified product may contain, in addition to the graft copolymer formed by alternate copolymerization of the styrenic vinyl monomer and the ⁇ , ⁇ -unsaturated carboxylic acid to a base resin of an ethylene/vinyl acetate copolymer, a copolymer produced by copolymerization of the styrenic vinyl monomer and the ⁇ , ⁇ -unsaturated carboxylic acid and furthermore an ethylene/vinyl acetate copolymer which does not undergo graft modification.
the adhesive of the present invention may be in the form of pellet, granule, powder, film or sheet.
the adhesive can contain antioxidants, light stabilizers, heat stabilizers, antistatic agents, fillers, antiblocking agents, etc., in addition to the said product, within such limits as may not impair the object of the present invention.
the adhesive of the present invention displays excellent bonding strength when applied to bond an ethylene/vinyl alcohol copolymer and polystyrene together, and laminated articles of ethylene/vinyl alcohol copolymer and polystyrene bonded with the adhesive of the present invention, for example, three-layer laminates consisting of an ethylene/vinyl alcohol copolymer and polystyrene and having the adhesive of the present invention as an interlayer, not only show strong resistance to delamination but also excel in processability, therefore being of value as a deep-draw forming material with enhanced gas barrier properties and utilizable as a preservation rigid container for foods, especially frozen foods.
the ethylene/vinyl alcohol copolymer which is one substrate in the present invention, is commercially available polymer materials (e.g. Eval®E and Eval®F, manufactured by Kuraray Co., Ltd. Japan) which are obtainable by copolymerization of ethylene (5 to 50 mole %) and vinyl acetate (50 to 95 mole %), followed by saponification of the resultant polymers.
Eval®E and Eval®F manufactured by Kuraray Co., Ltd. Japan
polystyrene which is another substrate there may be mentioned commonly used styrene homopolymers; copolymers made by copolymerizing styrene as the principal component and other polymerizable vinyl monomers; and impact-resistant polystyrenes formed by incorporating a rubber component, and so forth.
a process which comprises (a) forming an ethylene/vinyl alcohol copolymer material and polystyrene material into a sheet, respectively and sandwiching between the sheets an adhesive which comprises a modified ethylene/vinyl acetate copolymer obtained by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to an ethylene/vinyl acetate copolymer, followed by hot-pressing, or (b) co-extruding an ethylene/vinyl aochol copolymer material and polystyrene material together with an adhesive which comprises a modified ethylene/vinyl acetate copolymer obtained by graft-copolymerizing a styrenic vinyl monomer and an ⁇ , ⁇ -unsaturated carboxylic acid to an ethylene/vinyl acetate copolymer.
the adhesive is deposited on one of the sheets in the form of the film or melt-coated on the surface of one of the sheets, on which another sheet is put to prepare a sandwich with a middle layer of the adhesive.
the sandwich is hot-pressed at 180°-230° C. to prepare a laminate.
the ethylene/vinyl alcohol copolymer and polystyrene can be bonded together to one piece to obtain laminates, the interlayer of which is an adhesive of the present invention.
a co-extrusion die is used and the extrusion temperature of the polystyrene is about from 200° to 250° C., that of the ethylene/vinyl alcohol copolymer is from 200° to 230° C. and that of the modified ethylene/vinyl acetate copolymer is from 180° to 230° C.
the laminate sheet obtained by the above procedures usually consists of the polystyrene layer with a thickness of 200 to 800 ⁇ and the ethylene/vinyl alcohol copolymer with a thickness of 10 to 200 ⁇ and has an adhesive interlayer of 10 to 200 ⁇ .
the adhesive of the present invention is particularly useful as a co-extrudable adhesive in the co-extrusion method.
the ethylene/vinyl alcohol copolymer and xylene were charged into a Henschel mixer, and stirring was continued at 115° C. for 1 hour under a nitrogen atmosphere to dissolve completely the ethylene/vinyl acetate copolymer. Then, maleic anhydride and styrene were charged into the mixer, and after stirring for 10 minutes, a solution of a polymerization initiator in 100 ml of xylene was poured thereto, and the graft-copolymerization reaction was continued at 115° to 120° C. for 2 hours.
an ethylene/vinyl alcohol copolymer sheet (Eval®F, produced by Kuraray Co., Ltd.; thickness of 150 ⁇ ) and an impact-resistant polystyrene sheet (Styron®470, produced by Asahi Dow Co.; thickness of 150 ⁇ ) were laminated under a hot press of 200° C. to be 25 ⁇ in the bonding layer thickness to produce a laminate.
T-type peeling-off testing to measure peeling-off strength revealed that the laminate had 3.5 kg/cm of peeling-off strength.
Example 1 Following the same procedure as described in Example 1 except that they ethylene/vinyl acetate copolymer with a vinyl acetate content of 33 weight % and a melt index of 1 g/10 min. was used in Example 1 as ethylene/vinyl acetate copolymer, the graft copolymerization reaction was carried out to yield a modified ethylene/vinyl acetate copolymer with a melt index of 0.49 g/10 min. and maleic anhydride content of 20 weight %.
the modified copolymer was treated by the same procedure as described in Example 1 to produce a pellet-formed adhesive.
a laminate consisting of ethylene/vinyl alcohol copolymer and polystyrene sheets was prepared with use of the pellets as the adhesive layer.
the laminate showed 3.7 kg/cm of T-type peeling-off strength as measured.
the resins (a), (b) and (c) were individually melted in an extruder and each of the melted resins was fed to a three-layer co-extrusion die and co-extruded.
the extrusion temperature of the resin (a) was controlled to 210° C.
that of the resin (b) was controlled to 210° C.
that of the resin (c) was controlled to 200° C.
Resin (a) ethylene/vinyl alcohol copolymer (Eval®F; manufactured and marketed by Kuraray Co., Ltd.)
Resin (b) impact-resistant polystyrene (Styron®470; manufactured and marketed by Ashai Dow Co., Ltd.)
the procedure gave a three-layer laminate sheet consisting of layer (a) with a thickness of 60 ⁇ /layer (c) with a thickness of 40 ⁇ /layer (b) with a thickness of 290 ⁇ .
the laminate sheet obtained showed a 180° peeling strength of 2040 g/cm.
a vacuum draw forming technique a cylindrical cup was made of the laminate at 130° C. and in a draw ratio of 1. The delamination was not observed and the cup obtained had a good appearance.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Laminated Bodies (AREA)
Adhesives Or Adhesive Processes (AREA)
Graft Or Block Polymers (AREA)

US06/633,426 1983-07-22 1984-07-19 Laminated article and production thereof Expired - Fee Related US4576995A (en)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
JP58134649A JPS6026072A (ja)	1983-07-22	1983-07-22	変性エチレン・酢酸ビニル共重合体を含有してなる接着剤および該接着剤で接着した成型品
JP58-134649		1983-07-22

Publications (1)

Publication Number	Publication Date
US4576995A true US4576995A (en)	1986-03-18

Family

ID=15133304

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US06/633,426 Expired - Fee Related US4576995A (en)	1983-07-22	1984-07-19	Laminated article and production thereof

Country Status (4)

Country	Link
US (1)	US4576995A (de)
EP (1)	EP0133243A3 (de)
JP (1)	JPS6026072A (de)
KR (1)	KR920002981B1 (de)

Cited By (12)

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US4719153A (en) *	1984-11-12	1988-01-12	Kuraray Co., Ltd.	Laminated article and process for production thereof
US4861677A (en) *	1988-06-03	1989-08-29	E. I. Du Pont De Nemours And Company	Coextrudable adhesive for polystyrene, and products therefrom
US4861676A (en) *	1988-08-29	1989-08-29	E. I. Du Pont De Nemours And Company	Improved coextrudable adhesive and products therefrom
US5597865A (en) *	1994-11-21	1997-01-28	Quantum Chemical Corporation	Adhesive blends for polystyrene
US6183863B1 (en) *	1995-09-12	2001-02-06	Mitsui Chemical Inc	Adhesive ethylene copolymer resin compositions and laminates using the same
US6499878B1 (en)	1999-12-21	2002-12-31	Pactiv Corporation	Reclosable packages with barrier properties
US20040239241A1 (en) *	2003-05-30	2004-12-02	Georg Wittmann	Flexible multilayer packaging material and electronic devices with the packaging material
US7182986B1 (en) *	1998-07-09	2007-02-27	Kuraray Co., Ltd.	Container cap
US20070071988A1 (en) *	2005-09-29	2007-03-29	Botros Maged G	Adhesive blends for styrene polymers and articles
WO2019126189A1 (en)	2017-12-22	2019-06-27	E. I. Du Pont De Nemours And Company	Thermoplastic adhesive composition
WO2019126129A1 (en)	2017-12-22	2019-06-27	E. I. Du Pont De Nemours And Company	Thermoplastic adhesive composition
WO2019152830A1 (en)	2018-02-01	2019-08-08	Dow Silicones Corporation	Composition, polymer composite article formed therewith, and method of preparing same

Families Citing this family (5)

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Publication number	Priority date	Publication date	Assignee	Title
JPH0319088Y2 (de) *	1985-06-03	1991-04-23
US5089353A (en) *	1988-10-14	1992-02-18	Kuraray Co., Ltd.	Multi-layer material having gas barrier properties
EP0449654A3 (en) *	1990-03-30	1991-12-18	Mitsubishi Petrochemical Company Limited	Resin laminates
JP6563316B2 (ja) *	2014-11-28	2019-08-21	日本エイアンドエル株式会社	グラフト共重合体
JP6973166B2 (ja) *	2018-02-22	2021-11-24	Ｍｃｐｐイノベーション合同会社	接着性樹脂組成物、接着層及びそれを用いた積層体

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1983
- 1983-07-22 JP JP58134649A patent/JPS6026072A/ja active Pending
1984
- 1984-07-19 US US06/633,426 patent/US4576995A/en not_active Expired - Fee Related
- 1984-07-19 EP EP84108522A patent/EP0133243A3/de not_active Withdrawn
- 1984-07-21 KR KR1019840004327A patent/KR920002981B1/ko not_active Expired

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US3950209A (en) *	1972-06-13	1976-04-13	Toyo Soda Manufacturing Co., Ltd.	Process for preparing carboxylated polymer composition
US4102946A (en) *	1976-03-19	1978-07-25	Toyo Soda Manufacturing Co., Ltd.	Process for carboxylation of ethylene-vinyl acetate copolymers or saponified copolymers
US4157362A (en) *	1977-05-16	1979-06-05	Toyo Soda Manufacturing Co., Ltd.	Process for carboxylation of ethylene-vinyl acetate copolymers
JPS5446281A (en) *	1977-09-20	1979-04-12	Mitsubishi Petrochem Co Ltd	Manufacture of resin laminate
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4719153A (en) *	1984-11-12	1988-01-12	Kuraray Co., Ltd.	Laminated article and process for production thereof
US4861677A (en) *	1988-06-03	1989-08-29	E. I. Du Pont De Nemours And Company	Coextrudable adhesive for polystyrene, and products therefrom
EP0345069A3 (de) *	1988-06-03	1991-08-14	E.I. Du Pont De Nemours And Company	Coextrusionsfähiger Klebstoff für Styrolpolymere und damit hergestellte Gegenstände
US4861676A (en) *	1988-08-29	1989-08-29	E. I. Du Pont De Nemours And Company	Improved coextrudable adhesive and products therefrom
US5597865A (en) *	1994-11-21	1997-01-28	Quantum Chemical Corporation	Adhesive blends for polystyrene
US6183863B1 (en) *	1995-09-12	2001-02-06	Mitsui Chemical Inc	Adhesive ethylene copolymer resin compositions and laminates using the same
US6656601B1 (en)	1995-09-12	2003-12-02	Mitsui Chemicals Inc.	Adhesive ethylene copolymer resin compositions and laminates using the same
US7182986B1 (en) *	1998-07-09	2007-02-27	Kuraray Co., Ltd.	Container cap
US6499878B1 (en)	1999-12-21	2002-12-31	Pactiv Corporation	Reclosable packages with barrier properties
US20040239241A1 (en) *	2003-05-30	2004-12-02	Georg Wittmann	Flexible multilayer packaging material and electronic devices with the packaging material
US7535017B2 (en) *	2003-05-30	2009-05-19	Osram Opto Semiconductors Gmbh	Flexible multilayer packaging material and electronic devices with the packaging material
US20070071988A1 (en) *	2005-09-29	2007-03-29	Botros Maged G	Adhesive blends for styrene polymers and articles
WO2019126189A1 (en)	2017-12-22	2019-06-27	E. I. Du Pont De Nemours And Company	Thermoplastic adhesive composition
WO2019126129A1 (en)	2017-12-22	2019-06-27	E. I. Du Pont De Nemours And Company	Thermoplastic adhesive composition
WO2019152830A1 (en)	2018-02-01	2019-08-08	Dow Silicones Corporation	Composition, polymer composite article formed therewith, and method of preparing same
WO2019152829A1 (en)	2018-02-01	2019-08-08	Dow Silicones Corporation	Composition, polymer composite article formed therewith, and method of preparing same
US12269950B2 (en)	2018-02-01	2025-04-08	Dow Silicones Corporation	Composition, polymer composite article formed therewith, and method of preparing same

Also Published As

Publication number	Publication date
EP0133243A2 (de)	1985-02-20
KR850001267A (ko)	1985-03-18
KR920002981B1 (ko)	1992-04-11
EP0133243A3 (de)	1986-01-29
JPS6026072A (ja)	1985-02-08

Legal Events

Date	Code	Title	Description
1984-07-19	AS	Assignment	Owner name: TAKEDA CHEMICAL INDUSTRIES, LTD., 27, DOSHOMACHI 2 Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:NAKABAYASHI, MASAMITSU;FURUKAWA, YUZO;TASHIRO, AKIRA;REEL/FRAME:004289/0837 Effective date: 19840716 Owner name: TAKEDA CHEMICAL INDUSTRIES, LTD.,JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAKABAYASHI, MASAMITSU;FURUKAWA, YUZO;TASHIRO, AKIRA;REEL/FRAME:004289/0837 Effective date: 19840716
1988-12-09	FEPP	Fee payment procedure	Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY
1989-09-01	FPAY	Fee payment	Year of fee payment: 4
1993-10-19	REMI	Maintenance fee reminder mailed
1994-03-20	LAPS	Lapse for failure to pay maintenance fees
1994-05-31	FP	Lapsed due to failure to pay maintenance fee	Effective date: 19940323
2018-01-23	STCH	Information on status: patent discontinuation	Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

Publication	Publication Date	Title
US4576995A (en)	1986-03-18	Laminated article and production thereof
EP0100912B1 (de)	1987-06-03	Verwendung einer Schmelzklebstoff-zusammensetzung und mit ihr laminiertes Erzeugnis
US4595726A (en)	1986-06-17	N-alkyl methacrylate modified polypropylene
US5240525A (en)	1993-08-31	Method of fabricating a multilayer barrier packaging material
US4719153A (en)	1988-01-12	Laminated article and process for production thereof
JPH03506050A (ja)	1991-12-26	接着剤配合物および接着剤配合物からなる多層構造体
EP0146138A2 (de)	1985-06-26	Schmelzformmasse
US5114795A (en)	1992-05-19	Multilayered high barrier packaging materials method for the preparation thereof
US5178946A (en)	1993-01-12	Resin laminates
JPH0159107B2 (de)	1989-12-14
WO2019063836A1 (en)	2019-04-04	Improved adhesion of polyolefins to polyesters
US3950209A (en)	1976-04-13	Process for preparing carboxylated polymer composition
JPS6331385B2 (de)	1988-06-23
US4157362A (en)	1979-06-05	Process for carboxylation of ethylene-vinyl acetate copolymers
JPH0311270B2 (de)	1991-02-15
JP2783779B2 (ja)	1998-08-06	酸化珪素層とポリオレフィン層とを有する包装材料
JP4433592B2 (ja)	2010-03-17	接着性樹脂組成物および積層体
JP4485172B2 (ja)	2010-06-16	接着剤組成物
JPH02188B2 (de)	1990-01-05
JPH044353B2 (de)	1992-01-28
JPH0221939B2 (de)	1990-05-16
JPH04246446A (ja)	1992-09-02	接着性樹脂組成物
JP2951492B2 (ja)	1999-09-20	多層積層体
JPH0160417B2 (de)	1989-12-22
JPS6310606A (ja)	1988-01-18	変性オレフイン系重合体の製造方法